JUKE
1951
929
NOTES
TABLE I1 (Continued) Yield,
R
R'
%
n-CdHg n-CsHi
64 60
C2& n-C3Hi iso-C3Hi n-C4Hge 3-CHaO(CH2)3 %CHIS(CHz)3 n-C4Hg n-CaH7
73 47 31 54 41 44 82 48
n-CqHg IL-C~H; n-C3H7 ?,-CnHg
73 62 41 41
4-CI-3-CHaCsHa
n-CaH;
44
4-Cl-3-CHaCsH3 4-FCeH4 4-FC6H4
CzHb n-C3H: n-CnHg
30 43 52
M.P., "C.
Recryst. Solvent'
Formula
Analyses, % ' Calcd. Found C H C H 45 42 5 20 45 7 5 5 39 43 40 4 73 43 73 4 95
164-166 133-134
Dil. ethanol Dil. ethanol C~Hs-pet. ether 144-146 Dil. ethanol 127-129 Dil. ethanol 155-156 Dil. ethanol 115-117 Dil. ethanol 103-105 Dil. ethanol 135-137 Dil. ethanol 171-173 Dil. ethanol 201-203 CsHc-pet. ether 194-105 CeH6 144-146 Dil. ethanol 132-133 Dil. ethanol 146-148 Dil. ethanol C&-pet. ether SaHC03 reppt. 142-144 Dil. ethanol CsHs-pet. ether 153-155 Dil. ethanol 131-133 Dil. ethanol 103-104 Dil. ethanol
41 43 43 45 43 40 40 38
16 40 40 42 06 88 62 60
4 22 41 17 4 25 4 73 43 48 4 84 4 73 43 56 4 63
40 38 45 47
62 60 42 26
4 34
5 4 4 4 3
20 93 66 34 89
45 43 40 40 38
70 16 84 84 66
40 76 3 89 38 78 5 20 45 15 5 62 47 60
5 5 4 3 3
23 08 81 99 91
4 46
3 86 5 46 5 53
45 42 5 20 46 04 5 32 43 40 4 73 43 21 4 71 46 11 5 03 46 02 4 98 48 16 5 52 48 41 5 75
The petroleum ether used was the fraction boiling a t 60-71". Since prepared in this study, this compound has been reported in Accepted German Patent Specification F 18339 IVb/lZo (Dec. 27, 1956). The required amine has been reported by K. Schneider, Ann., 375, 245 (1910). In this present work it Tvas prepared by lithium aluminum hydride reduction of 3methylmercaptopropionitrile [C. D. Hurd and L. L. Gershbein, J . Am. Chem. Soc., 69,2328 (1947)l by the method of L H -4mundsen and L. S. Selson, J . Am. Chem. Soc., 73,242 (1951). Since prepared in this present investigation, this compound has been described in Accepted German Patent Specification F 18136 IVb/IZo (Sept. 27, 1956). e This compound has since been reported independently in Accepted German Patent Specification F 18659 IVb/lZo (Dec. 27, 1956).
Acknowledgment. The authors are grateful to W. L. Brown, G. M. Maciak, H. L. Hunter, and Miss Gloria Beckmaiin for the microanalyses. Pharmacological studies were under the direction of Dr. Mary Root. THELILLYRESEARCH LABORATORIES ELILILLY6: Co. INDIANAPOLIS 6, ISD.
17-dione (I) by using alkaline hydrogen p e r ~ x i d e . ~ The same procedure was used in attempt to obtain the corresponding epoxide from I7P-acetoxy-landrosten-3-one(III), but without success. Further attempts to obtain the epoxide of 111 were made using perbenzoic acid in chloroform solution and with peracetic acid in benzene. Modification5 of the method used for the epoxidation of I yielded the
Steroid Epoxides
R
R'
W.11.HOEHN Received January 3, 1958
l a , 2a-Epoxyandrostane-3,17-dione (II),I a compound useful in the determination of the structure of ruscogeniii,2 mas prepared from l-androstene-3,(1) (7. P. Striehel and C. Tamm, Helv. Chim. Acta, 37, 1094 (1954) for discussion of the configuration of 1,2epoxides. (2) ll'. It. Henn, F. Colton, and R. Pappo, J . d 4 n ~f'heni. . Soc., 79, 3920 (1957). For other references concerning the striicture of ruscogenin see A. L. Kussbaum, F. E. Carlon, D. Gould, E. P. Oliveto, E. B. Hershberg, M. L. Gilmorr, and W. Chamey, J. Am. Chenz. Soc., 79, 4814 (1957); TI. Burn, B Ellis, and V. Petrow, Proc. Chem. Sor., 119 (1959); H Lapin arid C. Sannie, Bull. soc. ch.lm., 1552 (1955).
R 0
I
./H
I11
I1 IV
'OCOCHI T' -
,/"
'..OH
~- -
VI
R' 0 /H 'OCOCH, ,TI
' \air
~
( 3 ) A . Rutenandt and H. l)mnenl)c~rg,no,., 69, I158 ( 1036).
(4) P. L. Julian, ST. Cole, E. K.AIepr, arid l
